JP6660647B1 - Resin packaging container having composite silicon oxide film or composite metal oxide film, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite silicon oxide film and a composite metal oxide film having excellent gas barrier properties and water vapor barrier properties in a resin packaging container and suppressing deterioration thereof. A composite silicon oxide film formed by using an atomic layer deposition method, the first silicon oxide film containing silicon dioxide as a main component and the first silicon oxide film, and the first silicon oxide film. And a second silicon oxide film having a higher density than that of the silicon oxide film, and the second silicon oxide film has a photoelectron spectrum different from that of the first silicon oxide film. [Selection diagram] Fig. 1

Description

The present invention relates to a resin packaging container having a composite silicon oxide film or a composite metal oxide film , and a method for producing the same.

  In recent years, resin packaging containers have been used in various fields, but resin containers are lighter and have lower transportation costs than metal containers and glass containers, and have excellent impact resistance, There is a disadvantage that the gas barrier property and the water vapor barrier property are inferior. In particular, in resin containers for high-grade cosmetics and resin containers containing chemicals whose quality is strictly controlled, containers having excellent gas barrier properties and water vapor barrier properties are required even at a certain cost (Patent Document 1, 2).

  The inventors of the present application have disclosed in Japanese Patent No. 5795427 (Patent Document 3) that a metal oxide film (silicon oxide) having a thickness of 5 nm to 100 nm is formed on an inner surface and / or an outer surface of a resin container by using atomic layer deposition (ALD). A resin container with excellent gas barrier properties has been developed by forming a film. The ALD method has a drawback that it takes time to form a film, but is excellent in that a uniform metal film can be formed on a container having a complicated shape, and is suitable for forming a small lot and a variety of high-grade resin containers. This is the optimal technology.

However, the metal oxide film (silicon oxide film) formed by the above-described invention can maintain excellent gas barrier properties immediately after the film formation or when it is stored and managed in an unused state, but the contents such as water and ethanol can be maintained. If the metal oxide film is continued to be used in a state in which the metal oxide film is kept, the formed metal oxide film is deteriorated after several weeks to several months, and it is difficult to maintain a desired gas barrier property, and it cannot be put to practical use.

As a metal oxide film, it is conceivable to use an aluminum oxide film (alumina film) with excellent gas barrier properties and water vapor barrier properties in a resin container, but in pharmaceuticals, foods, cosmetics, etc., the contents may directly touch the alumina film. Therefore, it is necessary to perform some coating on the alumina film using an arbitrary method. For example, when a silicon dioxide film is coated on an alumina film using a normal ALD method, there is a problem that the silicon dioxide film is easily deteriorated and peeled off as described above. Furthermore, although it is possible to perform coating by application instead of the ALD method, it is difficult to completely apply the resin inside a resin container having a complicated shape, which is not practical and is not practical.

Further, when an alumina film is used for a resin container, it is difficult to remove the alumina film, and there is a problem in recycling the resin container.

JP 2014-65198 A JP 2009-228661 A Patent No. 5795427

The present invention solves the above-mentioned problems, and does not deteriorate for a long time even by contact with the contents, and provides a composite silicon oxide film or a composite metal oxide film capable of maintaining excellent gas barrier properties and water vapor barrier properties. It is an object to provide a resin-made packaging container having the same.

In order to achieve the above object, a first invention of the present application is a resin packaging container having an inner surface and / or an outer surface of a composite silicon oxide film on which an atomic layer is deposited, wherein silicon dioxide is a main component. A first silicon oxide film, and a second silicon oxide film formed on the first silicon oxide film and having a higher density structure than the first silicon oxide film;
The second silicon oxide film has a different photoelectron spectrum from the first silicon oxide film,
Has a peak in the range of 102.3 eV to 103.3 eV,
A structure of SiOx (2 <x), wherein the thickness of the first silicon oxide film is 18.0 nm or more, more preferably 30.0 nm or more, and the thickness of the second silicon oxide film is 0.6 nm or more. , Characterized in that.

To achieve the above object, a second aspect of the present invention is a resin-made packaging container having the inner surface and / or outer surface of the composite metal oxide film atomic layer is deposited, the composite metal oxide The film is a base layer composed of a metal oxide film selected from the group consisting of aluminum, gallium, germanium, titanium, zirconium, and zinc; and a first silicon oxide formed on the base layer and containing silicon dioxide as a main component. A second silicon oxide film formed on the first silicon oxide film, wherein the second silicon oxide film has a higher density structure than the first silicon oxide film and has a different photoelectron spectrum. A film having
Has a peak in the range of 102.3 eV to 103.3 eV,
It has a structure of SiOx (2 <x), the thickness of the base layer is 2.0 nm or more, more preferably 5.0 nm or more, and the thickness of the first silicon oxide film is 18.0 nm or more, more preferably 30 nm or more. 0.02 nm or more, and the thickness of the second silicon oxide film is 0.6 nm or more.

Further, the third and fourth inventions of the present application are a method of forming the composite silicon oxide film and the composite metal oxide film of the first and second inventions in a resin packaging container. I do.

According to the resin packaging container of the first invention of the present application, the second silicon oxide film having a higher density structure than the first silicon oxide film is formed on the first silicon oxide film, so that contact with the contents is achieved. The gas barrier property can be maintained for a long time without deterioration, and the excellent gas barrier property can be maintained. Further, the excellent water vapor barrier property can prevent the content from volatilizing from the container surface to the outside. In addition, the silicon oxide film formed on the resin container can be easily peeled off as compared with other metal oxide films, and thus is suitable for recycling the resin container.

Further, according to the resin packaging container according to the second invention of the present application, as the composite metal oxide film, aluminum, gallium, germanium, titanium, zirconium, and a base layer made of a metal oxide film selected from the group consisting of zinc, and Forming a first silicon oxide film, and further forming a second silicon oxide film having a higher density structure than the first silicon oxide film on the first silicon oxide film. The gas barrier property is exhibited, and the volatilization of the content to the outside is further suppressed by the more excellent water vapor barrier property, and these effects can be maintained for a longer time.

  Further, according to the second invention of the present application, a base layer made of a metal oxide film selected from the group consisting of aluminum, gallium, germanium, titanium, zirconium, and zinc, and a first silicon oxide film thereon, By forming the second silicon oxide film having a higher density structure than the first silicon oxide film, although there is a problem in recycling the resin container, it exhibits more excellent gas barrier properties and more excellent water vapor barrier. The volatility of the content to the outside can be further suppressed by the property, and these effects can be maintained for a longer period of time.

  In addition, film formation for resin packaging containers used for pharmaceuticals, foods, cosmetics, and the like is required to be colorless and harmless to the human body. Although there are many applicable metal oxide films other than the silicon oxide film, many metal oxide films are not colorless if they are too thick and look rainbow or white in some cases due to light interference. For these reasons, a silicon oxide film is most preferable from these points, and there is no problem in cost.

Sectional view of the composite silicon oxide film according to the first embodiment of the present invention Sectional view of the composite metal oxide film according to the second embodiment of the present invention Sectional view of a film formed on a resin packaging container (first embodiment) Schematic diagram of an apparatus for forming a silicon oxide film on a resin container Schematic diagram of steam gas generator and activation device Graph of photoelectron spectrum using XPS

Hereinafter, embodiments of the present invention will be described in detail.
FIG. 1 schematically shows the structure of the composite silicon oxide film according to the first embodiment of the present invention. A first silicon oxide film 101 containing silicon dioxide as a main component is formed on the surface of a resin container 100 by atomic layer deposition (ALD), and a second oxide film having a higher density than the first silicon oxide film 101 is formed thereon. A silicon film 102 is also formed by atomic layer deposition (ALD).

  Note that the silicon oxide film illustrated in FIG. 1 illustrates an example of a two-layer structure including a first silicon oxide film 101 and a second silicon oxide film 102, and further includes a first silicon oxide film 101 and a second silicon oxide film 102. May be repeatedly formed to form a four-layer structure, a six-layer structure, or the like. For the respective film thicknesses, see the examples described later.

  FIG. 2 schematically shows the structure of the composite metal oxide film according to the second embodiment of the present invention. A base layer 103 made of an aluminum oxide film (alumina film) is formed on the surface of the resin container 100 by an atomic layer deposition method (ALD), and a first silicon oxide film 101 is further formed thereon by an atomic layer deposition method (ALD). After that, a second silicon oxide film 102 having a higher density than the first silicon oxide film 101 is formed thereon.

  The material of the base layer 103 can be at least one metal oxide selected from the group consisting of gallium, germanium, titanium, zirconium, and zinc, in addition to aluminum.

  The first silicon oxide film 101 and the second silicon oxide film 102 in the second embodiment show an example of a two-layer structure as in the first embodiment, but the first silicon oxide film 101 and the second silicon oxide film The film 102 may be repeatedly formed to have a total five-layer structure or a seven-layer structure combined with the base layer. Alternatively, the three-layer structure including the base layer may be a six-layer structure, a nine-layer structure, or the like, which is repeatedly formed. For the respective film thicknesses, see the examples described later.

The first silicon oxide film according to the first embodiment and the second embodiment is SiO2, but the second silicon oxide film is formed of SiOx (2 <2) that is denser and denser than the first silicon oxide film. x) . Hereinafter, the manufacturing method will be described.

  The first silicon oxide film according to the first embodiment and the second embodiment is SiO2, but the second silicon oxide film is SiOx (1 ≦ 1) formed more densely and densely than the first silicon oxide film. x ≦ 3) and x ≠ 2. Hereinafter, the manufacturing method will be described.

  The composite silicon oxide film and the composite metal oxide film according to the present invention are formed by an atomic layer deposition (ALD) apparatus schematically shown in FIG. A resin container 100 which is an object to be processed is placed in the reaction container 1. In actual production, a large number of containers are accommodated in the reaction container 1 and processed in batches. The reaction vessel 1 is connected to an exhaust pump 2, and exhausts gas filling the reaction vessel 1 through an exhaust pipe 3. Further, a first metal gas container 4 is connected to the reaction container 1 through a first flow rate controller 5 as a supply unit for supplying a metal gas for silicon film formation. A second metal gas container 6 is connected through a second flow controller 7 as a supply unit for supplying a metal gas such as aluminum used in a second embodiment described below. Further, a steam or oxygen gas generator 8 is connected through a activating device 9 or 10 as a plasma gas supply means for supplying a gas obtained by exciting a gas containing water vapor or oxygen by plasma.

  FIG. 5 is a schematic diagram of a steam gas generator and an activation device. In the apparatus, the inert gas can be humidified by introducing an inert gas from the left side and passing water through the humidifier 11. Argon gas is used as the inert gas. The humidified argon gas generates a plasma in a region 14 by a high-frequency magnetic field applied by an inductive coil 13 in a glass tube 12, and generates an activated water vapor by passing through the region, thereby causing a reaction. It is sent to the container 1. For example, the electromagnetic energy applied by the inductive coil 13 is 20 W and the frequency is 13.56 MHz.

A second silicon oxide film 102 is further formed on the first silicon oxide film 101 formed in the above-described process. The method is to increase the power for generating plasma in the above-described process, or It is formed by extending the time for introducing excited water vapor or oxygen. The formed second silicon oxide film is a denser and denser film than the first silicon oxide film 101, and has a structure of SiOx (2 <x) .

  A second silicon oxide film 102 is further formed on the first silicon oxide film 101 formed in the above-described process. The method is to increase the power for generating plasma in the above-described process, or It is formed by extending the time for introducing excited water vapor or oxygen. The formed second silicon oxide film is a denser and denser film than the first silicon oxide film 101, and has a structure of SiOx (1 ≦ x ≦ 3) and x ≠ 2.

  The first silicon oxide film 101 and the second silicon oxide film 102 are both silicon oxide films, but have a difference in photoelectron spectrum as shown in FIG. FIG. 6A is a photoelectron spectrum observed using X-ray photoelectric spectroscopy (XPS). A dotted line indicates the first silicon oxide film 101 and a solid line indicates the second silicon oxide film 102.

The first silicon oxide film 101 and the second silicon oxide film 102 are formed on the same substrate, and the substrate is subjected to an Ar etching process for 10 minutes to remove the silicon oxide film on the surface, thereby forming the second silicon oxide film. The film 102 was removed, and the photoelectron spectrum of the first silicon oxide film 101 was measured. At the same time, FIG. 6B shows a measurement result of a substrate composed of only the first silicon oxide film 101 for comparison. A similar Ar etching process was performed for only the first silicon oxide film 101, and the film structure was compared by removing the surface film. In the drawing, the solid line represents the surface and the dotted line represents the internal measurement value after etching.

  FIG. 6B, which is formed only by the first silicon oxide film 101, shows that the shape of the spectrum centered at 103.2 eV does not change even when the film on the surface is removed by Ar etching. In a), it can be seen that the shape of the spectrum changes due to the removal of the second silicon oxide film 102 and changes to a peak centered at 103.2 eV as in FIG. 6B. Therefore, it can be seen that the second silicon oxide film 102 has a peak in the range from 102.3 eV to 103.3 eV indicated by the solid line in FIG.

  The spectrum of the second silicon oxide film 102 shown by the solid line in FIG. 6A is composed of a combination of a plurality of silicon spectra, and has a strong peak at 102.8 eV. The difference is due to the difference in the state of the chemical bond around the silicon atom, and it can be seen that the chemical shift is performed in the direction of higher density.

  As described above, by forming the denser and higher-density second silicon oxide film 102 on the first silicon oxide film 101 formed on the surface of the resin container 100, excellent gas barrier properties and water vapor barrier properties are obtained. And the deterioration of the film due to the contact with the contents in the container can be reduced.

  In addition, the resin used as the raw material of the resin container is not particularly limited, and examples thereof include polyethylene, polypropylene, polyethylene terephthalate, polystyrene, acrylonitrile styrene, polyvinyl chloride, cycloolefin polymer, and olefin copolymer.

  The method for forming the composite metal oxide film according to the second embodiment is basically the same as the apparatus and method for forming the composite silicon oxide film according to the first embodiment, but before forming the first silicon oxide film. At least one metal oxide film (base layer 103) selected from the group consisting of aluminum, gallium, germanium, titanium, zirconium, and zinc is formed on the surface of the resin container 100, and then the same as in the first embodiment. The first silicon oxide film 101 and the second silicon oxide film 102 are formed by a method.

  Based on each of the first embodiment and the second embodiment, below, several examples were created, a test was performed to compare with a comparative example, and gas barrier performance, water vapor barrier performance, and film degradation performance were compared. .

  In addition, in the case of a resin-made packaging container that contains medicines, foods, and cosmetics as contents, the oxygen permeability immediately after production is at least 0.002 (cc / pkg · day · atm) or less. It is required that the oxygen permeability after three months has passed is at least 0.004 (cc / pkg · day · atm). In this test, the content change rate (water vapor barrier property) after 3 months has passed is required to be at least 1.0% or less. These numerical values are referred to as reference value 1, reference value 2, and reference value 3, respectively. Further, in special medicines, foods, cosmetics, etc., gas barrier properties and water vapor barrier properties far higher than the above-mentioned reference values are required. It is possible to form a composite film having a high gas barrier property and a water vapor barrier property far exceeding 3 to 3.

(Preparation of Examples 1 to 9)
Using the atomic layer deposition (ALD) apparatus shown in FIG. 4, the first silicon oxide film 101 shown in FIG. 1 , which is the first embodiment, is repeatedly formed at a deposition rate of 0.06 nm / cycle by a required number of times. A resin container 100 having the first silicon oxide film 101 of 18 nm, 30 nm, and 54 nm was formed. The resin container 100 for forming a film is made of polyethylene terephthalate resin.

  In this example, tris (dimethylamino) silane was used as a metal gas. The temperature of the resin container 100 was 23 ° C.

  The first silicon oxide film 101 is formed on both the inner surface and the outer surface of the container, has a substantially uniform thickness over the entire surface, and is not easily attached by plasma CVD or the like. It was confirmed that the film had a uniform film thickness even at the corners.

  Next, the time for introducing the water vapor activated by the plasma into the resin container 100 on which the 18 nm, 30 nm, and 54 nm first silicon oxide films 101 were formed was doubled, and the film formation rate was 0.06 nm / The cycle was repeatedly formed as many times as necessary, and a second silicon oxide film 102 having a thickness of 0.6 nm, 3.0 nm, and 4.8 nm was further formed, and the resins of Examples 1 to 9 shown in Table 1 were formed. A container was obtained.

(Preparation of Comparative Examples 1 to 7)
Comparative Example 1 was a resin container made of polyethylene terephthalate, on which no film was formed, used in Examples 1 to 9.

Comparative Example 2 was a resin container in which only the same silicon oxide film as the first silicon oxide film 101 was formed to a thickness of 30 nm in the same polyethylene terephthalate resin container as in Examples 1 to 9.

Comparative Example 3 was a resin container in which only the aluminum oxide film 103 was formed to 8 nm in the same polyethylene terephthalate resin container as in Examples 1 to 9.

Comparative Example 4 in which a first silicon oxide film 101 and a second silicon oxide film 102 were formed thinner than in Examples 1 to 9 in a polyethylene terephthalate resin container similar to Examples 1 to 9, respectively. And

  Further, in the same polyethylene terephthalate resin container as in Examples 1 to 9, the first silicon oxide film 101 was set to 102 nm, and the second silicon oxide film 102 was the same as that in Examples 1 to 9; 6 and 7.

(Comparative test 1)
The oxygen permeability of the resin containers according to Examples 1 to 9 and Comparative Examples 1 to 7 was measured using a multi-sample oxygen permeability measuring device OX-TRAN 2/61 (manufactured by MOCON). The measurement was performed using air as the test gas under a 23 ° C., 60% RH environment (23 ° C., 0% RH inside the container), and a jig equipped with a nitrogen gas inlet tube and a discharge tube at the mouth of the container. And 10 cc / min. Of nitrogen from the inlet tube. And the amount of oxygen contained in the nitrogen discharged from the discharge pipe was measured. The measurement results are the permeability (cc / pkg · day · atm) per resin container. The results are shown in Table 1.

  As shown in Table 1, in Examples 1 to 9, the oxygen permeability immediately after production (or in a non-use state as a container) far exceeded the reference value 1 described above, and pure oxygen without a metal oxide film was provided. It can be seen that the oxygen permeability is significantly improved as compared with Comparative Example 1 which is a resin container. Further, as in Examples 4 to 9, by increasing the thickness of the first silicon oxide film to 30 nm or more, the oxidative transmittance can be further improved.

  Note that Comparative Example 2 consisting of only the first silicon oxide film had excellent gas barrier properties immediately after production, but was inferior in degradation performance as shown in Comparative Tests 2 and 3 below. It is clear from the test results that the aluminum oxide film has high gas barrier properties.

  Further, at the level of the thin film of Comparative Example 4, there is a problem in actual use, and at the level of the thick film of Comparative Examples 5 to 7, on the contrary, the quality of the film used for a general resin container is excessive. Therefore, there is a problem in manufacturing cost.

(Comparative test 2)
The resin containers according to Examples 1 to 9 and Comparative Examples 1 to 7 were filled with water and subjected to an acceleration test at a normal quadruple speed for 3 months in a thermostat set at 50 ° C. (theoretically). 12 month test), and their oxygen permeability was compared. Table 2 shows the results.

  As shown in Table 2, the composite silicon oxide films according to Examples 1 to 9 satisfy the above-described reference value 2 of the gas barrier property even in a state of being filled with water for 3 months (theoretical 12 months). The deterioration rate (the ratio of the permeability after the test to the oxygen permeability immediately after production) of Examples 1 to 8 is less than 10, and the deterioration rate (deterioration speed) can be suppressed.

  Note that Comparative Example 2 consisting of only the first silicon oxide film has excellent gas barrier properties immediately after production, but is inferior in deterioration performance. In Comparative Examples 5 to 7, since the first silicon oxide film is considerably thick, the gas barrier property is excellent, but the deterioration rate is large, and the effect is smaller than the cost required for film formation.

  In addition, the level of the thin film of Comparative Example 4 was lower than the reference value 2, and there was a problem in actual use.

(Comparative test 3)
The resin containers of Examples 1 to 9 and Comparative Examples 1 to 7 were subjected to an acceleration test at a normal quadruple speed for 3 months in a constant temperature bath filled with a 70% aqueous ethanol solution and set at 50 ° C. (theory) And the oxygen permeability was compared in the same manner as in Test Example 1. Table 3 shows the results.

  As shown in Table 3, the composite silicon oxide films according to Examples 1 to 9 satisfy the above-described reference value 2 of the gas barrier property even in a state of being filled with the aqueous ethanol solution for three months (theoretically, 12 months). The deterioration rate (the ratio of the oxygen permeability after the test to the oxygen permeability immediately after production) of Examples 1 to 8 is less than 10, and the deterioration rate (deterioration speed) can be suppressed.

(Comparative test 4)
The resin containers of Examples 1 to 9 and Comparative Examples 1 to 7 were filled up to 80% of the containers with a 70% aqueous ethanol solution, and then the mouth was sealed with an aluminum cap. Thereafter, an acceleration test at a normal quadruple speed is performed for 3 months in a constant temperature bath at 40 ° C. (a theoretical 12-month test), and the weight is measured and compared with the weight before the start of the test. I asked. The results are shown in Table 4. The change in the total weight is caused by the content (water) evaporating to the outside of the container through the container wall.

  As shown in Table 4, in the composite silicon oxide films according to Examples 1 to 12, the weight loss rate in a state filled with the aqueous ethanol solution satisfies the above-described reference value 3 for 3 months (theoretically 12 months), This indicates that the barrier property is high. It can be seen that when only the first silicon oxide film having a considerable thickness as in Comparative Example 2 or the composite film as in Comparative Example 4 is thin, the water vapor barrier property is inferior.

Note that, as described above, Comparative Examples 4 to 7 are slightly inferior to the barrier properties compared to Examples 1 to 9 or increase costs due to excessive film formation. In some cases, even Comparative Examples 4 to 7 can be put to practical use. That is, Examples 1 to 9 are merely standard film formation models, and it goes without saying that Comparative Examples 4 to 7 may be examples of the present invention.

(Examples 10 to 15)
Using an atomic layer deposition (ALD) apparatus shown in FIG. 4, a resin container in which aluminum oxide films of 2 nm, 5 nm, 8 nm, 20 nm, 30 nm, and 40 nm were formed as the base layer 103 shown in FIG. Produced. The resin container 100 is made of polyethylene terephthalate resin. The atomic deposition rate of the aluminum oxide film is 0.1 nm per cycle.

  The same 30 nm first silicon oxide film and 4.8 nm second silicon oxide film as in Example 6 were further formed on the resin container on which the aluminum oxide films of 2 nm, 5 nm, 8 nm, 20 nm, 30 nm and 40 nm were formed. The resulting resin containers were prepared as Examples 10, 11, 12, 13, 14, and 15, respectively.

(Comparison)
The following tests were performed using the above-mentioned Example 6 having no base layer 103 as a comparative object.

(Comparative test 5)
As in Comparative Test 1, the oxygen permeability of the resin containers according to Examples 10 to 13 and Comparative Examples 8 and 9 was measured using a multi-sample oxygen permeability measuring device OX-TRAN 2/61 (manufactured by MOCON). did. The measurement was performed in a 23 ° C., 60% RH environment (23 ° C., 0% RH inside the container) as in Comparative Test 1, and a jig equipped with a nitrogen gas inlet and outlet tube was attached to the mouth of the container. Using air as a test gas, nitrogen was introduced at 10 cc / min. And the amount of oxygen contained in the nitrogen discharged from the discharge pipe was measured. The measurement results are the permeability (cc / pkg · day · atm) per resin container, and the results are shown in Table 5.

  In Examples 10 to 15 described above, since the base layer has an aluminum oxide film having a sufficient gas barrier property even by itself, it far exceeds the reference value 1, and thus the first silicon oxide film and the second silicon oxide film. It can be seen that the gas barrier properties are much higher than in Example 6 comprising a film.

Further, Comparative Examples 6, 7, and 8 were performed on Examples 10 to 15 as in Comparative Examples 2 to 4. The results are shown in Tables 6, 7, and 8. In Tables 6 to 8, comparisons with Example 6 were also made.

  Since the aluminum oxide film originally has a high water vapor barrier property in addition to the gas barrier property, as shown in Tables 6, 7, and 8, Examples 10 to 15 each having a structure of a base layer + a first silicon oxide film + a second silicon oxide film. All have much more excellent functions than those of Example 6, and it can be seen that the above reference values 1 to 3 are easily cleared.

  As described above, Examples 10 to 15 are composite metal oxide films applied to special resin containers requiring extremely high gas barrier properties and water vapor barrier properties, and are used as resin containers having a so-called standard gas barrier property. The composite silicon oxide films of Examples 1 to 9 exhibit sufficient effects. In Examples 10 to 15, since the first silicon oxide film + the second silicon oxide film were formed on the aluminum oxide film, the first silicon oxide film and the aluminum oxide film could be easily formed even after long-term use. There is no peeling.

(Examples 16 to 19)
In Examples 16 to 19, the zinc oxide film was used as the base layer instead of the aluminum oxide film used in the above Examples 10 to 15, and the thickness of the zinc oxide film was set to 5, 8, 20. The first silicon oxide film was formed to 30 nm and the second silicon oxide film was formed to 4.8 nm on each of the zinc oxide films. Note that the atomic deposition rate of the zinc oxide film is 0.2 nm per cycle.

Tests 9, 10, 11, and 12 similar to the above-described comparative tests were performed on each of the resin containers of Examples 10 to 15. The results are shown in Tables 9, 10, 11, and 12.

Although the performance using the zinc oxide film as the base layer is slightly lower than the performance using the aluminum oxide film, the gas barrier property and the water vapor barrier property are higher than those of the silicon oxide film. As shown in the examples, Examples 16 to 19 each having the structure of the base layer + the first silicon oxide film + the second silicon oxide film have excellent functions, and easily clear the above reference values 1 to 3. You can see that it is.

  In Examples 10 to 19, the most standard aluminum oxide film and zinc oxide film were formed as the base layers. However, in addition to these metal films, a gallium oxide film, a germanium oxide film, and a titanium oxide film were used. A film, a zirconium oxide film, or the like may be used, and similar effects can be obtained.

  As described above, according to the first invention of the present application (including Examples 1 to 9 and Comparative Examples 4 to 7), the composite silicon oxide film including the first and second silicon oxide films having different structures and characteristics is employed. By doing so, it is possible to obtain a metal oxide film that can exhibit high gas barrier properties and water vapor barrier properties over a long period of time without using an aluminum oxide coating that is often avoided as a film for a resin packaging container, Oxidation of the contents and volatilization outside the container can be largely suppressed. Further, since the resin container can be easily separated from the resin container, it is suitable for recycling the resin container.

  According to the second invention (Examples 10 to 19) of the present application, a composite having two types of silicon oxide films according to the first invention on a metal oxide film (aluminum oxide film, zinc oxide film, etc.). By adopting a metal oxide film, it is possible to protect special contents by a resin container by having higher gas barrier properties and water vapor barrier properties as compared with the first invention.

  Note that the metal oxide film exhibiting gas barrier properties includes various organic metal compounds that are gasified, such as a compound in which carbon is directly bonded to a metal, a compound in which carbon is bonded through oxygen, and a compound in which carbon is bonded through nitrogen. All compounds that can be used and can be used in conventional atomic layer deposition methods are applicable. Examples of the organic metal gas include, for example, organic silicon compounds such as trimethylaminosilane and bisdimethylaminosilane, organic zirconium compounds such as trimethylamidozirconium, organic titanium compounds such as titanium isopopropoxide and titanium dimethylethylaminotitanium, and organic compounds such as trimethylgallium. Gallium compounds, organozinc compounds, organogermanium compounds, organoaluminum compounds such as trimethylaluminum and the like can be cited, and in particular, silicon oxide films are used for resin-made packaging containers containing chemicals, foods, cosmetics, and the like as contents. It is preferable that the present invention is an invention specializing in the silicon oxide film.

DESCRIPTION OF SYMBOLS 1 Reaction container 2 Exhaust pump 3 Exhaust pipe 4 First metal gas container 5 First flow controller 6 Second metal gas container 7 Second flow controller 8 Steam or oxygen gas generator 9, 10 Activator 11 Humidifier 12 Glass tube 13 Inductive coil 14 Plasma generation area 100 Resin container (resin layer)
101 first silicon oxide film 102 second silicon oxide film 103 base layer

Claims (7)

A resin packaging container having a composite silicon oxide film on which an atomic layer is deposited on an inner surface and / or an outer surface,
The composite silicon oxide film,
A first silicon oxide film containing silicon dioxide as a main component, and a second silicon oxide film formed on the first silicon oxide film and having a higher density structure than the first silicon oxide film;
The second silicon oxide film has a different photoelectron spectrum from the first silicon oxide film,
Has a peak in the range of 102.3 eV to 103.3 eV,
A structure of SiOx (2 <x),
The thickness of the first silicon oxide film is 18.0 nm or more, preferably 30.0 nm or more, and the thickness of the second silicon oxide film is 0.6 nm or more.
A resin packaging container having a composite silicon oxide film. The composite silicon oxide film includes a plurality of the first silicon oxide films and the second silicon oxide films alternately formed.
A resin packaging container having the composite silicon oxide film according to claim 1. A resin packaging container having a composite metal oxide film having an atomic layer deposited on its inner surface and / or outer surface,
The composite metal oxide film ,
Aluminum, gallium, germanium, titanium, zirconium, and a base layer composed of an oxide film of a metal selected from the group consisting of zinc,
A first silicon oxide film formed on the base layer and containing silicon dioxide as a main component;
A second silicon oxide film formed on the first silicon oxide film;
The second silicon oxide film has a higher density structure than the first silicon oxide film, and has a different photoelectron spectrum,
Has a peak in the range of 102.3 eV to 103.3 eV,
A structure of SiOx (2 <x),
The thickness of the base layer is 2.0 nm or more, preferably 5.0 nm or more,
The thickness of the first silicon oxide film is 18.0 nm or more, preferably 30.0 nm or more, and the thickness of the second silicon oxide film is 0.6 nm or more.
A resin packaging container having a composite metal oxide film. The composite metal oxide film includes a plurality of the first silicon oxide films and the second silicon oxide films alternately formed on the base layer.
A resin packaging container having the composite metal oxide film according to claim 3. In the composite metal oxide film, three layers of the base layer, the first silicon oxide film, and the second silicon oxide film are repeatedly formed in the same order.
A resin packaging container having the composite metal oxide film according to claim 3. A method of forming a composite silicon oxide film on a resin packaging container by using an atomic layer deposition method,
A step of depositing a first silicon oxide film containing silicon dioxide as a main component in an atomic layer on the packaging container in the reaction container; and forming a structure having a higher density than the first silicon oxide film on the first silicon oxide film. Considerably depositing a second silicon oxide film having an atomic layer,
The second silicon oxide film has a different photoelectron spectrum from the first silicon oxide film,
Has a peak in the range of 102.3 eV to 103.3 eV,
A structure of SiOx (2 <x),
The thickness of the first silicon oxide film is 18.0 nm or more, more preferably 30.0 nm or more, and the thickness of the second silicon oxide film is 0.6 nm or more.
A method of forming a composite silicon oxide film on a resin packaging container. A method of forming a composite metal oxide film on a resin packaging container by using an atomic layer deposition method,
In the reaction vessel, aluminum, gallium, germanium, titanium, zirconium, and a step of depositing an atomic layer of a base layer constituted by an oxide film of a metal selected from the group consisting of zinc,
Depositing an atomic layer of a first silicon oxide film containing silicon dioxide as a main component on the base layer; and forming a second oxide film having a higher density structure on the first silicon oxide film than the first silicon oxide film. The process of depositing a silicon film in atomic layers and
The second silicon oxide film has a higher density structure than the first silicon oxide film, and has a different photoelectron spectrum,
Has a peak in the range of 102.3 eV to 103.3 eV,
A structure of SiOx (2 <x),
The thickness of the base layer is 2.0 nm or more, more preferably 5.0 nm or more,
The thickness of the first silicon oxide film is 18.0 nm or more, more preferably 30.0 nm or more, and the thickness of the second silicon oxide film is 0.6 nm or more.
A method for forming a composite metal oxide film on a packaging container made of resin, characterized by comprising: